CN104277007A - Method of synthesizing 5,5'-bistetrazole-1,1'-dioxodihydroxy ammonium salt - Google Patents
Method of synthesizing 5,5'-bistetrazole-1,1'-dioxodihydroxy ammonium salt Download PDFInfo
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- CN104277007A CN104277007A CN201310288601.2A CN201310288601A CN104277007A CN 104277007 A CN104277007 A CN 104277007A CN 201310288601 A CN201310288601 A CN 201310288601A CN 104277007 A CN104277007 A CN 104277007A
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- C07D257/00—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms
- C07D257/02—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms not condensed with other rings
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Abstract
The invention discloses a method of synthesizing a 5,5'-bistetrazole-1,1'-dioxodihydroxy ammonium salt. The method comprises the following step: synthesizing the 5,5'-bistetrazole-1,1'-dioxodihydroxy ammonium salt by taking dichloroglyoxime, sodium azide, sodium hydroxide and hydroxylamine hydrochloride as raw materials and adopting alcohol solvents by virtue of azidation reaction, acid catalysis cyclization reaction and salt forming reaction. Compared with the prior art, the two-step reaction adopted by the method disclosed by the invention only adopts one solvent, so that not only can type of solvents be reduced, but also the after-treatment process of the azidation reaction can be cancelled. Meanwhile, the types of catalytic acids are expanded, the difficulty of the production process is lowered, the total yield of the reaction is increased, and thus, the method is an efficient and low-cost synthetic method.
Description
Technical field
The present invention relates to a kind of novel insensitiveness high energy compound-5,5 '-(molecular formula is C to bis-tetrazolium-1,1 '-dioxy two hydroxyl ammonium salt
2h
8n
10o
4) new synthetic method.This energy-containing compound can not only realize the target as the green surrogate of conventional explosives RDX, and performance is much better than RDX; Simultaneously because its high nitrogen content can also realize substituting gas generator propellant component triaminoguanidinium nitrate (TAGN) etc.
Background technology
Researchist has carried out research widely to the design of novel energetic compounds, and the difference of everybody research is that the mode of the interior energy of increase taked is different.
The energy of tradition energetic material RDX, TNT comes from the oxidation of the oxygen in molecule to backbone carbon atoms; Ring or cage modle tension link compound ONC, TNAZ further increase energy due to the introducing of ring strain and high Enthalpies of Formation; And the energy of high nitrogen compound mainly comes from nitrogen nitrogen double bond and nitrogen nitrogen singly-bound is converted into nitrogen.
Being below the structural formula of part energy-containing compound, is reductibility group in circle, and circle is outer is reactive species:
TNT RDX ONC TNAZ
But these energy-containing compounds have some defects: aromatic nitro and nitramine have certain toxicity; Too much ring and the general synthetic route of cage modle tension compound longer (cost is high); Thermostability and mechanical stability will be caused to reduce when nitrogen-atoms number on each ring of high nitrogen compound or chain increases.
Think that the method for a possible solution high nitrogen compound stability is at present: on nitrogen system, increase zwitterionic N-oxide group, remove ó cloud density energy stable molecule, increase density and oxygen balance, thus cause energy to increase.In addition, the N-of polarity is oxidized key and adds intermolecular interaction, usually can increase the stability of these materials for physical shock, makes it can safe handling.Be below the structural formula of N-oxidation base height nitrogen compound:
The design of novel high-energy material needs to consider academic nature, practicality and technical advance simultaneously.In order to find the novel high-energy material of more high-performance, safer, cheap and environmental protection, energetic material chemistry needs the computer modeling technique of novel compound, new synthesis strategy and advanced person.High nitrogen class novel high-energy thing Quality Research, needs the preparation method developing new N-N key binding reaction and new heterocyclic system, needs exploitation simple and safe and the synthetic route of applicable amplification.
The high nitrogen-containing of tetrazole ring and high Enthalpies of Formation are the bases of high-energy performance, tetrazole ring is introduced N-O structure and can generate the new compound of a class--the oxygen balance of higher density and stability, lower sensitivity and improvement.5,5 '-bis-tetrazolium-1,1 '-dioxy two hydroxyl ammonium salt Enthalpies of Formation Δ fH is 447kJ/mol, density 1.88g/cm
3, decomposition temperature 221 ° of C, sensitivity is lower than RDX, and performance is much better than RDX, almost can replace current most of general explosive.
The people such as the NikoFischer of external current mainly Univ Munich Germany study the synthetic method of 5,5 '-bis-tetrazolium-1,1 '-dioxy two hydroxyl ammonium salt.
Concrete synthetic route is as follows at present, (A) 5,5 '-bis-tetrazolium oxidative synthesis 5,5 '-bis-tetrazolium-1,1 '-dioxy two hydroxyl ammonium salt; (B) two nitrine glyoxime Cyclization 5,5 '-bis-tetrazolium-1,1 '-dioxy two hydroxyl ammonium salt.
Approach A: adopt peroxidation sulfuric acid hydrogen aqueous solutions of potassium oxidation 5,5 '-bis-tetrazolium, obtain two kinds of isomerss (1,1 '-dihydroxyl-5,5 '-bis-tetrazolium and 2,2 '-isomer), wherein isomer 1, the productive rate of 1 '-dihydroxyl-5,5 '-bis-tetrazolium is only 11%.The 5-nitro that the people such as method and the NikoFischer of peroxodisulphate oxidation 5,5 '-bis-tetrazolium report is identical with the method for oxidation of 5-azido-tetrazolium.But the primary product that this preparation method obtains is 2,2 '-isomer isomer (58%), only obtain little 1,1 '-dihydroxyl-5,5 '-bis-tetrazolium isomer (11%), add 5,5 '-bis-tetrazolium-1, the 1 '-dioxy dihydroxy ammonium salt product obtained after aqueous hydroxylamine continues reaction corresponding also little.
The people such as Tselinskii report the novel method that one carries out two nitrine glyoxime cyclization synthetic intermediate 1,1 '-dihydroxyl-5,5 '-bis-tetrazoliums in acid condition.Glyoxime by oxalic dialdehyde, oxammonium hydrochloride, sodium hydroxide prepared below 10 DEG C; Dichloroglyoxime is occurred in ethanol by glyoxime that chlorination reaction obtains, and productive rate is 85%; Two nitrine glyoximes, by dichloroglyoxime, chloro-nitrine permutoid reaction occur in DMF to be prepared, and productive rate is more than 80%.Starting raw material is oxalic dialdehyde, and it is four steps that reactions steps is kept to by five steps, neutralizes four steps isolate 5 through oximate, chlorination, nitrine cyclisation and azanol, 5 '-bis-tetrazolium-1,1 '-dioxy two hydroxyl ammonium salt.
But this method needs repeatedly to use different solvents instead, particularly uses a large amount of ether, have the scale that adds and amplify the danger of producing, employ hydrogen chloride gas as catalyzer, add the difficulty of product aftertreatment.
Summary of the invention
The object of the present invention is to provide a kind of synthesis 5 newly, 5 '-bis-tetrazolium-1, the method of 1 '-dioxy two hydroxyl ammonium salt, to reduce synthesis cost, to improve reaction efficiency and product yield, final batch production insensitiveness energy-containing compound 5,5 '-bis-tetrazolium-1,1 '-dioxy two hydroxyl ammonium salt, advances its design ap-plication.
Solution of the present invention is: with dichloroglyoxime, sodiumazide, sodium hydroxide, oxammonium hydrochloride for raw material, adopt alcoholic solvent, by azido reaction, acid catalysis annulation and hydroxylamination Reactive Synthesis 5,5 '-bis-tetrazolium-1,1 '-dioxy two hydroxyl ammonium salt.Reaction formula is as follows:
The present invention for raw material, adopts alcoholic solvent, by azido reaction, acid catalysis annulation with become salinization Reactive Synthesis 5,5 '-bis-tetrazolium-1,1 '-dioxy two hydroxyl ammonium salt with dichloroglyoxime, sodiumazide, sodium hydroxide, oxammonium hydrochloride.
Described azido reaction is that take alcohols as solvent, under-40 ~ 40 DEG C of temperature condition, carry out azido reaction, reaction 0.5-24 hour, obtains azido reaction liquid stand-by with dichloroglyoxime and sodiumazide for raw material; The feed molar proportioning of described dichloroglyoxime and sodiumazide is 0.1:1-1:10, and the feed molar proportioning of alcoholic solvent and dichloroglyoxime is 0.1:1-1:10.
Described acid catalysis annulation is: add azido reaction liquid in a reservoir, to reaction solution cooling-40 ~ 20 DEG C, add in reaction solution while stirring or pass into acid catalyst, temperature of reaction condition-40 ~ 20 DEG C, reaction 1-24 hour, after completion of the reaction, system rises to room temperature naturally, after purification processes, obtains intermediate product 1,1 '-dihydroxyl-5,5 '-bis-tetrazolium; Dichloroglyoxime metering in the reaction of more than usage quantity of described acid catalyst step, the feed molar proportioning of acid and dichloroglyoxime is 0.1:1-1:10.
Described acid catalyst is one or more in mineral acid, organic acid, solid super-strong acid.
Described acid catalyst is one or more in hydrogenchloride, the vitriol oil or polystyrene sulfonic acid type resin.
Described one-tenth salinization reaction is: with intermediate product 1,1 '-dihydroxyl-5,5 '-bis-tetrazolium, reacts with sodium hydroxide and hydroxylamine hydrochloride solution respectively, obtain 5,5 '-bis-tetrazolium-1,1 '-dioxy dihydroxy ammonium salt product.
Azido reaction of the present invention and acid catalysis annulation all use same alcoholic solvent.Described acid catalyzed reaction no longer introduces new organic solvent, but directly the mixture system of azido reaction is carried out catalyzed reaction, decreases aftertreatment technology.
Alcoholic solvent of the present invention is the straight chain and the branched alkyl alcohol that contain 1 ~ 10 carbon atom.
Alcoholic solvent of the present invention is methyl alcohol, ethanol, Virahol, ethylene glycol.
The present invention's advantage is compared with prior art:
(1) compared with external existing bibliographical information, azido reaction and the acid catalysis annulation of present method only used a kind of solvent, reduce reaction solvent kind, reduce raw materials cost.
(2) eliminate the aftertreatment technology of azido reaction, directly the reaction solution after azide is carried out acid catalysis annulation.Compared with reporting with similar document, decrease the aftertreatment technology of azido reaction, improve combined coefficient, shorten synthesis cycle, reduce synthesis cost.
(3) two-step reaction is merged into successive reaction, overall yield is increased to about 85% by 50.3%, reduce further synthesis cost.
Provided by the invention 5,5 '-bis-tetrazolium-1,1 '-dioxy two hydroxyl ammonium salt synthetic method, is that a kind of efficiency is high, yield is high, cost is low, easy-operating synthetic method, expands the kind of catalysis acid simultaneously, reduce producting process difficulty.Adopting 5,5 '-bis-tetrazolium-1,1 '-dioxy two hydroxyl ammonium salt of the method synthesis, when not changing reaction solvent, its overall yield can be made to get a promotion, cost reduces, and enhances its synthesized competitiveness as insensitiveness energy-containing compound.
Specific embodiments
Embodiment 1:
Dichloroglyoxime 156.0g(1.0mol is added in 2000ml there-necked flask), add 1000ml methanol solvate.After the methanol solution of dichloroglyoxime is cooled to-40 DEG C, start to drip 65.0g(1.0mol in solution in batches) sodiumazide, starts stirring.After adding, react 0.5 hour, slowly go up to room temperature.Reaction liquid after azide is cooled to-40 DEG C, passes into hydrogenchloride, react 1 hour.Through purification processes, obtain intermediate product 1,1 '-dihydroxyl-5,5 '-bis-tetrazolium, by 1,1 '-dihydroxyl-5,5 '-bis-tetrazolium is dissolved in 500ml water, add 50g sodium hydroxide, stirring reaction, then add the reaction of 50g oxammonium hydrochloride, obtain 5,5 '-bis-tetrazolium-1,1 '-dioxy two hydroxyl ammonium salt 212.5g, productive rate is 90%.
Embodiment 2: add dichloroglyoxime 312.0g(2mol in 2000ml there-necked flask), add 1000ml propylene glycol solvent.After 0 DEG C is cooled to the propylene glycol solution of dichloroglyoxime, in solution, add 117.0g(1.8mol) sodiumazide, starts stirring.After adding, react 10 hours, slowly rise to room temperature.By the reaction liquid insulation after azide at 40 DEG C, drip 98% vitriol oil 1L, react 15 hours, through purification processes, obtain intermediate product 1,1 '-dihydroxyl-5,5 '-bis-tetrazolium, by 1,1 '-dihydroxyl-5,5 '-bis-tetrazolium is dissolved in 1000ml water, adds 100g sodium hydroxide, stirring reaction, add the reaction of 100g oxammonium hydrochloride again, obtain 5,5 '-bis-tetrazolium-1,1 '-dioxy two hydroxyl ammonium salt 401.5g, productive rate is 85%.
Embodiment 3:
Dichloroglyoxime 7.8kg(50mol is added in 50L reactor), add 30L alcohol solvent.After the ethanolic soln of dichloroglyoxime is cooled to 20 DEG C, start to add 3.8kg(60mol in solution) sodiumazide, starts stirring.After adding, react 24 hours, slowly rise to room temperature.Reaction liquid after azide is cooled to 0 DEG C, adds polystyrene sulfonic acid type resin 10L, stir 24 hours, through purification processes, obtain intermediate product 1,1 '-dihydroxyl-5,5 '-bis-tetrazolium, by 1,1 '-dihydroxyl-5,5 '-bis-tetrazolium is dissolved in 20L water, adds 1kg sodium hydroxide, stirring reaction, add the reaction of 1kg oxammonium hydrochloride again, obtain 5,5 '-bis-tetrazolium-1,1 '-dioxy two hydroxyl ammonium salt 9.45kg, productive rate is 80%.
Claims (9)
1. a synthesis 5,5 '-bis-tetrazolium-1, the method of 1 '-dioxy two hydroxyl ammonium salt, it is characterized in that: with dichloroglyoxime, sodiumazide, sodium hydroxide, oxammonium hydrochloride for raw material, adopt alcoholic solvent, by azido reaction, acid catalysis annulation and salt-forming reaction synthesis 5,5 '-bis-tetrazolium-1,1 '-dioxy two hydroxyl ammonium salt.
2. synthesis 5 according to claim 1,5 '-bis-tetrazolium-1, the method of 1 '-dioxy two hydroxyl ammonium salt, it is characterized in that described azido reaction is for raw material with dichloroglyoxime and sodiumazide, take alcohols as solvent, under-40 ~ 40 DEG C of temperature condition, carry out azido reaction, reaction 0.5-24 hour, obtains azido reaction liquid stand-by; The feed molar proportioning of described dichloroglyoxime and sodiumazide is 0.1:1-1:10, and the feed molar proportioning of alcoholic solvent and dichloroglyoxime is 0.1:1-1:10.
3. the method for synthesis 5,5 '-bis-tetrazolium-1,1 '-dioxy two hydroxyl ammonium salt according to claim 1 and 2, is characterized in that: described alcoholic solvent is the straight chain and the branched alkyl alcohol that contain 1 ~ 10 carbon atom.
4. the method for synthesis 5,5 '-bis-tetrazolium-1,1 '-dioxy two hydroxyl ammonium salt according to claim 3, is characterized in that: described alcoholic solvent is one or more in methyl alcohol, ethanol, Virahol, ethylene glycol.
5. synthesis 5 according to claim 1 and 2,5 '-bis-tetrazolium-1, the method of 1 '-dioxy two hydroxyl ammonium salt, it is characterized in that described acid catalysis annulation is: add azido reaction liquid in a reservoir, to azido reaction liquid cooling but-40 ~ 20 DEG C, add in reaction solution while stirring or pass into acid catalyst, temperature of reaction condition-40 ~ 20 DEG C, reaction 1-24 hour, after completion of the reaction, system rises to room temperature naturally, after purification processes, obtain intermediate product 1,1 '-dihydroxyl-5,5 '-bis-tetrazolium; Dichloroglyoxime metering in the reaction of more than usage quantity of described acid catalyst step, the feed molar proportioning of acid and dichloroglyoxime is 0.1:1-1:10.
6. the method for synthesis 5,5 '-bis-tetrazolium-1,1 '-dioxy two hydroxyl ammonium salt according to claim 5, is characterized in that: described acid catalyst is one or more in mineral acid, organic acid, solid super-strong acid.
7. the method for synthesis 5,5 '-bis-tetrazolium-1,1 '-dioxy two hydroxyl ammonium salt according to claim 5, is characterized in that: described acid catalyst is one or more in hydrogenchloride, the vitriol oil or polystyrene sulfonic acid type resin.
8. synthesis 5 according to claim 1,5 '-bis-tetrazolium-1, the method of 1 '-dioxy two hydroxyl ammonium salt, it is characterized in that: described one-tenth salinization reaction intermediate product 1,1 '-dihydroxyl-5,5 '-bis-tetrazolium, react with sodium hydroxide and hydroxylamine hydrochloride solution respectively, obtain 5,5 '-bis-tetrazolium-1,1 '-dioxy dihydroxy ammonium salt product.
9. the method for synthesis 5,5 '-bis-tetrazolium-1,1 '-dioxy two hydroxyl ammonium salt described in claim 1 or 2, is characterized in that: described acid catalysis annulation no longer introduces new organic solvent, directly the mixture system of azido reaction is carried out catalyzed reaction.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104829548A (en) * | 2015-03-30 | 2015-08-12 | 北京理工大学 | 5, 5 '-bistetrazole-1, 1'-dioxo hydroxylammonium salt synthetic method |
| TWI667222B (en) * | 2018-07-31 | 2019-08-01 | 國家中山科學研究院 | Preparation method of low sensitivity and high energy explosive |
| CN111153864A (en) * | 2020-01-17 | 2020-05-15 | 西北大学 | Nitrogen-rich heat-resistant insensitive energetic compound and preparation method and application thereof |
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| US6156906A (en) * | 1998-12-28 | 2000-12-05 | Japan Hydrazine Co., Inc. | Process for the preparation of 5,5'-bi-1H-tetrazole salt |
| CN101508681A (en) * | 2008-08-19 | 2009-08-19 | 阜新奥瑞凯精细化工有限公司 | Method of preparing high purity tetrazole ammonium salt |
| WO2013026768A1 (en) * | 2011-08-19 | 2013-02-28 | Ludwig-Maximilians-Universität München | Energetic active composition comprising a dihydroxylammonium salt or diammonium salt of a bistetrazolediol |
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2013
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US6156906A (en) * | 1998-12-28 | 2000-12-05 | Japan Hydrazine Co., Inc. | Process for the preparation of 5,5'-bi-1H-tetrazole salt |
| CN101508681A (en) * | 2008-08-19 | 2009-08-19 | 阜新奥瑞凯精细化工有限公司 | Method of preparing high purity tetrazole ammonium salt |
| WO2013026768A1 (en) * | 2011-08-19 | 2013-02-28 | Ludwig-Maximilians-Universität München | Energetic active composition comprising a dihydroxylammonium salt or diammonium salt of a bistetrazolediol |
Non-Patent Citations (2)
| Title |
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| I. V. TSELINSKII等: "Synthesis and Reactivity of Carbohydroximoyl Azides: I. Aliphatic and Aromatic Carbohydroximoyl Azides and 5-Substituted 1-Hydroxytetrazoles Based Thereon", 《RUSSIAN JOURNAL OF ORGANIC CHEMISTRY》 * |
| NIKO FISCHER等: "Pushing the limits of energetic materials-the synthesis and characterization of dihydroxylammonium 5,5’-bistetrazole-1,1’-diolate", 《JOURNAL OF MATERIALS CHEMISTRY》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104829548A (en) * | 2015-03-30 | 2015-08-12 | 北京理工大学 | 5, 5 '-bistetrazole-1, 1'-dioxo hydroxylammonium salt synthetic method |
| TWI667222B (en) * | 2018-07-31 | 2019-08-01 | 國家中山科學研究院 | Preparation method of low sensitivity and high energy explosive |
| US11161795B2 (en) | 2018-07-31 | 2021-11-02 | National Chung-Shan Institute Of Science And Technology | Method for preparation of insensitive high explosive |
| CN111153864A (en) * | 2020-01-17 | 2020-05-15 | 西北大学 | Nitrogen-rich heat-resistant insensitive energetic compound and preparation method and application thereof |
| CN111153864B (en) * | 2020-01-17 | 2021-06-29 | 西北大学 | Nitrogen-rich heat-resistant insensitive energetic compound and preparation method and application thereof |
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